Process for separating mercaptans



Patented July 12, 19 38 UNITED STATES PATENT OFFICE son Givens, Berkeley, Development Compan CaliL, assignors to Shell San Francisco, Calif a corporation of Delaware No Drawing; Application September 5, 1936, Serial No. 99,636

3 Claims.

This invention relates to the removal of mercaptans from their solutions in organic liquids .and in particular deals with the sweetening of gasoline distillates by treating same with solid 5 substantially anhydrous cadmium hydroxide in the absence of strongly alkaline-reacting substances such as caustic.

It is known that cadmium hydroxide when suspended in an alkaline medium, such as aqueous sodium hydroxide, ammonia, etc. is capable of effecting sweetening of sour hydrocarbons such as gasoline or kerosene distillates, i. e. by removing mercaptans therefrom to an extent so that the distillates react negatively to the so-called Doc- 15 tor test.

- In many instances, however,.tr eatment of organic liquids with alkaline-reacting substances has disadvantages. For instance, such treatments render cracked gasoline distillates less gumand color-stable, due to the removal of acidreacting hydroxy aromatic compounds which act as gum inhibitors. Certain solvents for mercaptans, such as lower alcohols, being misciblewlth alkali hydroxides or ammonia, particularly in the presence of water, cannot be treated therewith, while still other solvents of the type of aldehydes, etc. tend to polymerize in the presence of alkalies. Moreover, emulsiondifficulties frequently prevent the application of aqueous'alkalies.

On the other hand, in the absence of water soluble alkaline substances, cadmium hydroxide was heretofore considered incapable of effectively removing mercaptans from their solutions in organic solvents such as liquid hydrocarbons, and I 35 therefore the advantages offered by the knowntreating methods involving the use of cadmium hydroxide over ordinary caustic treatment were relatively small;

.We now have discoveredthat mercaptans can be removed from their solutions, in the absence of strongly alkaline-reacting substances, by treatment with cadmium hydroxide, provided the latter is substantially anhydrous, i. e. contains less than about 30% free moisture and preferably less than about The term strongly alkalinereacting substance as herein used refers to strong bases such as alkali hydroxides, the alkaline earth oxides and hydroxides, ammonium hydroxide, quaternary ammonium bases, etc., any one of which when in aqueous solution is capable of extracting hydroxy aromatic compounds of the type of phenol,'xylenol, etc. from their organic solutions. The reason for the difference in behavior between aqueous and anhydrous cadmium hydroxide is believed to be due to the fact, that degree. The spent reagent is then allowed to cadmium hydroxide is preferentially wetted by water, so that when it is contacted in the wet state with a treating solution, such as a sour gasoline distillate, little actual contact between the hydroxide and the gasoline distillate takes place, 5

with the result that-only a very small amount of cadmium mercaptides forms within a reasonable period of time, usually insuificient to eiiect a precipitation of mercaptides. The higher the moisture content of the cadmium hydroxide the more slowly does it react with the mercaptans in the organic solution. If the moisture content is about 30 or 40% or higher, the rate of reaction is too slow for practical use. a. r In the absence of water, however, cadmium hydroxide is readily wetted by gasolineor other organic solvents containing the mercaptans, and cadmium mercaptides can form and precipitate more rapidly.

Anhydrous cadmiumv hydroxide isa fine white powder which is non-injurious, is easily handled,

- for instance, by mechanical blowers, and presents none of the difliculties which are characteristic of alkaline substances. Mechanically the greatest difiiculty is occasio ned .by its fineness which at times may retard settling or cause it to run through filters. Such difliculties can be overcome by employing basket centrifuges, filter aids such as kieselguhr, electrical precipitation means, etc. Our process is normally carried out by adding the required amount of substantially anhydrous cadmium hydroxide to a batch of mercaptan so-, lution and agitating the mixture until the mere captan content has been reduced to the desired settle and the supernatant solvent is drawn ofi; or the mixture is simply filtered.

Another method consists of introducing into'a suitable treating vessel an amount of cadmium hydroxide to form a filter bed and continuously passing through this bed the mercaptan solution at a sufiiciently low rate to eifect the desired mercaptan removal. If some of the reagent is carried ofiin suspension by the stream of liquid, the suspended matter may be settled out n a suitable settling vessel. The flow of merca tan solution through the bed may be continued until the reagent is spent, i. 'e. the mercaptan solution is no longer being desulfurized to the desired degree.

A third practical method consists of continuously feeding cadmium hydroxide or a slurry thereof in a suitable "organic solvent which is preferably at least-partially miscible with the. treating solution, into an agitator together with not be less than 1, part of the materials number of carbon molecules. the formation of high carbon di-mercaptides dethe treating solution, agitating the resulting mixmal room temperatures although higher or lower temperatures may be employed. a

The amount .of cadmium hydroxide required can be calculated, if the concentration of the mercaptans in the solution is known. For'successi'ul mercaptan removal the molal ratio of cadmium hydroxide to mercaptan should, in general, reacting according to the equation RSH+Cd(OH) 2 Cd( OH) SR-i-HzO but the main reactionbeing While most of the lower cadmium mercaptides, i. c. those containing not more than about carbon atoms are substantially insoluble in organic solvents and particularly in liquid hydrocarbons, we have found that higher mercaptides may be soluble therein to a considerable extent. As a general rule, the solubility of the mercaptides increases with the number of carbon atoms and the branching of the carbon chain. The following-rough rule between number of carbon atoms in cadmium mercaptides and their solubility in hydrocarbon liquids has been established: mercaptides of mercaptans containing 6 and less carbon atoms are substantially insoluble in organic solvents and thus can be separated substantially completely; to separate mercaptans having '7 to 10 carbon atoms by means of cadmium hydroxide special means may be required as will hereinafter be explained; and mercaptans having more than 10 carbon atoms frequently form mercaptides of solubilities too great for complete separation. a

Since solubility of mercaptides increases with the number of carbon atoms, it is desirable that the formation of di-mercaptides be suppressed as much as possible. This can be partly achieved,

by treating the mercaptan solution with an amount of cadmium hydroxide which is in excess of the molal proportion of reagent to mercaptan- However, a. certain amount of di-mercaptides seems to form regardless of the excess of reagent, so that thisprecaution alone is insuflicient.

Another .means for minimizing the number of carbon atoms in the mercaptides is to suppress the formation of di-mercaptides in which both mercaptide radicals have a comparatively high The probability of pends upon the relative concentration of lower and higher mercaptans- By increasing the concentration of lower over higher mercaptides this probability is reduced. Thus by adding to the 'mercaptan solution containing relatively high mercaptans a correspondingly substantial proportion of low mercaptans such as ethyl, propyl,

butyl mercaptans, .we can considerably increase the efficacy of our mercaptan separation. The

secondary and tertiary low mercaptans seem to be especially useful for this purpose as-may be seen from the following example:

Samples of a gasoline containing .0128% mercaptan sulfur of mercaptans having 6 and more carbon atoms were treated with equi-rnolalqua'ntities of cadmium hydroxide before and after.

adding lower mercaptans. 100 milliliters of each treated sample wereevaporated and ashed to from 150 determine the amount of dissolved mercaptides. The results were as follows:

Total mer- Residual as Mercaptan added captan sulfur Cd 0 mg.

- in solution per 100 ml.

None 0128 14. 4 Ethyl mercaptan 0410 3. 8 Isopropyl mercaptan 0430 1. 8 Normal butyl mercaptan..- 0503 3. 8 Secondary butyl mercaptan 0533 2. 2 Tertiary butyl mcrcaptau 0476 0.0

Another method of removing soluble cadmium mercaptides from their solutions consists of treating themfwith non-acid adsorption agents such as charcoal, magnesium hydroxide, etc. The adsorbent may be added together with the cadmium hydroxide, or the cadmium hydroxide treated liberate relatively large amounts of free mercaptans, and therefore should not be applied. The effectiveness of non-acid adsorbents is illustrated in the following example of treating a West Texas straight run gasoline:

Mcrcaptan or Treating reagent mercaptide in Doctor" test treated solution None 0818 Sour. Gd(OH), .0500 Sweet. Mg(OH); 0600 Sour. Cd(0B):+Mg(OH)2-- ..0032 Slightly sour.

While our treating method is generally applicable to mercaptan solutions in organic substantially non-acid solvents as hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, aldehydes, ketones, nitrohydrocarbons, aminohydrocarbons. alkylcyanides, etc. or various combinations of such solvents, it is of particular value when applied to the sweetening of gasoline distillates. As has been indicated hereinbefore, other treating methods capable of actually removing mercaptans, such as caustic treatment, also remove the acid-reacting natural gum inhibitors, while other sweetening treatments merely convert mercaptans to di-sulfides. It is well known that the removal of mercaptans is preferable to their conversion to di-sulfides, since di-sulfldes adversely afiectthe antiknock value and lead susceptibility of gasolines. natural gum inhibitors is very desirable as is illus trated by the following example.

Samples of a cracked gasoline fraction boiling to '200" C. were sweetened with Doctor solution, cadmium hydroxide suspended lowing results:

Copper dish Induction sweetening reagent period gugloglglper None 4hr. 35 min 111 "Doetor solution -2 hr. 50 min 54 Cadmium hydroxide in caustic 3 hr. min 38 solution.

Anhydrous cadmium hydroxide..." 6 hr. 10 min.-. 1

On the other hand, the retention of The induction period is the time to which the gasoline may be exposed to 100 lbs. oxygen pressure at 100 C. until spontaneous absorption of oxygen begins. The induction periodis a..meas-' ure for the storage stability of the gasoline.

often fractionally distill a gasoline to be sweetened to produce a lighter fraction boiling below about 175 0. containing mercaptans and usually hydrogen sulfide, but which is substantially free mal end boiling point of gasolines, which besides rom natural gum inhibitors, and a heavier frac tion boiling between about 175 C. and the inor- "containlng mercaptans is an inhibitor concentrate free from hydrogen sulfide. The light fraction is sweetened by any convenient method preferably one which is capable of removing mercaptans, for instance, by extraction with aqueous caustic containing less than 50% water or a mixture of aqueous caustic and a suitable solubility promoter for mercaptans such as ethanol amine, ethylene diamine, quaternary ammonium bases, etc. The heavier fraction is treated with anhydrous cadmium hydroxide with or without the addition of a non-acid adsorption agent. After removal of the treating reagents the fraction, if still slightly sour, may be oxidized in any suitable manner to convert last traces of mercaptans to di-sulfides. The fully sweetened heavier fraction, containing the natural gum inhibitors, may then be blended with 1 the sweetened light fraction to produce a balanced, sweet and stabilized gasoline of good lead susceptibility.

Elimination of hydrogen sulfide and carboxylic acids from gasoline distillates prior to treatment with cadmium hydroxide is desirable, preferably by treating in a manner to avoid substan tial removal of natural gum inhibitors, for instance, by suitably fractionally distilling and/or treating with non-alkaline or weakly alkaline reagents such as tripotassium phosphate, sodium arsenite, lead oxide, iron oxidepetc. Hydrogen sulfide is preferentially absorbed by cadmium hydroxide, thereby consuming same, and the separation of mercaptans cannot proceed until it has been removed, while carboxylic acids tend to form oil soluble cadmium salts, which would cause the loss of cadmium hydroxide aside from introducing into the gasoline a compound which upon combustion forms an undesirable ash.

Cadmium hydroxide is most easily regenerated from the mercaptides by dissolving thelatter in a dilute acid, such as sulfuric, and then precipitating the hydroxide by making the solution slightly alkaline. The precipitated cadmium hydroxide is filtered and dried under conditions substantially to prevent its conversion to the oxide, the latter being ineffective for separation of mercaptans. Suitable drying temperatures are about 100 to I10 0. at normal atmospheric pressures. I,

We claim as our invention: 1. In the process of separating mercaptans contained in a solution of an organic solvent for mercaptans which is liquid and. substantially inert to cadmium hydroxide under the conditions of the treatment, the steps of reacting the dissolved mercaptans at substantially normal room temperature with a solid reagent free from acidic and strongly alkaline reacting substances whose only active component consists of cad- 3 mium hydroxide containing less than 30% water, and separating products of reaction from the solvent.

2. In the process of separating mercaptans contained in a solution of an organic solvent for mercaptans which is liquid and substantially inert to cadmium hydroxide under the conditions of the treatment, the steps of suspending in said solution at substantially normal room temperature a solid reagent free from acidic and.

strongly alkaline reacting substances whose only ctive component consists of cadmium hydroxide containing less than 30% water, thereby reacting the mercaptans with the cadmium hydroxide,

and separating products of reaction from the 'solvent.

3. In the process of separating mercaptans contained in a solution of a hydrocarbon distillate, the steps of contacting said distillate at substantially normal room temperature with a solid reagent free from acidic and strongly alkaline reacting substances whose only active component consists of cadmium hydroxide containing less than 30% water, thereby reacting the mercaptans with the cadmium hydroxide,

and separating products of reaction from the distillate.

4. In 'the process of separating mercaptans contained in a solution of an organic solvent for mercaptans which is liquid and substantially inert to cadmium hydroxide under the conditions of the treatment, the steps of suspending in said solution at substantially normal room temperature a solid powder consisting of cadmium hydroxide containing less than 10% water, thereby reacting mercaptans with the cadmium hydroxide, and separating products of reaction from the solvent.

'5. In the process of separating mercaptans contained in a solution of an organic solvent for mercaptans which is liquid and substantially inert to cadmium hydroxide under the conditions of the treatment, the steps of reacting the dissolved mercaptans at substantially-normal room temperature with an amount of a solid reagent free from acidic and strongly alkaline reacting substances whose only active component consists of cadmium hydroxide containing less than 30% water, said amount containing at least one mol. of cadmium hydroxide per mol. mercaptans in the solution, and separating products of reaction from the solvent.

6. In the process of separating mercaptans contained in a solution of an organic solvent for mercaptans which is liquid and substantially inert to cadmium hydroxide under the conditions of the treatment, the steps of suspending in said solution at substantially normal room temperature a solid reagent free from acidic and strongly alkaline reacting substances whose only active component consists of cadmium hydroxide containing less tha n 30% water, and a separate solid adsorbent co mprising magnesium hydroxide, thereby reacting mercaptans with the cadmium hydroxide, and separating products of reaction from the solvent.

7. In the process of separating mercaptans contained in a solution of an organic solvent component consists of cadmium hydroxide con-- tainln: less than 30% water, and a separate solid adsorbent consisting oi magnesium hydroxide, thereby reacting mercaptans with the cadmium hydroxide, and separating products of reaction 5 irom the solvent.

lornium hydroxide under the conditions of the treatment, the steps o! dissolvingin said solution mercaptans of less than 5 carbon atoms and contacting the resulting mercaptan enriched solution at substantially normal room temperature with a solid reagent free from acidic and strongly alkaline reacting substances whose only active component consists of cadmium hydroxide containing less than 30% water, thereby reacting merca'ptans with the cadmium hydroxide, and separating products of reaction from the solvent.

DAVID LOUIS YABROFF. JOHN WILKINSON GIVENS. v 

